Smart Adhesion Research Articles

Cohesion Regulation of Polyphenol Cross‐Linked Hydrogel Adhesives: From Intrinsic Cross‐Link to Designs of Temporal Responsiveness

AbstractPolyphenol hydrogels have found widespread application in wound healing, bone repair, drug delivery, and biosensors due to their robust wet adhesion, high ductility, and excellent self‐healing ability. However, these hydrogels often exhibit low intrinsic cohesion, which limits their overall adhesive strength. Enhancing cohesion is critical for improving both the adhesion and mechanical properties of the hydrogels, thereby expanding their utility in biomedical fields. This review begins by exploring strategies to enhance the cohesion of polyphenol hydrogel adhesives, detailing modifications that act individually or synergistically. The importance of temporally regulating cohesion is emphasized to accommodate various applications and environmental conditions. Finally, this paper discusses remaining challenges in cohesion regulation and outlines prospects for future research. It is hoped that this comprehensive review will provide new insights into the development of advanced polyphenolic hydrogel adhesives and contribute to the design of “smart adhesives” for increasingly complex needs in biomedical applications.

Strong, Spontaneous, and Self-Healing Poly(Ionic Liquid) Elastomer Underwater Adhesive with Borate Ester Dynamic Crosslinking.

Adhesion in aqueous environments is often hindered by the water layer on the surface of the substrate due to the water sensitivity of the adhesive, greatly limiting the application environment. Here, a borate ester dynamically crosslinked poly(ionic liquid) elastomer adhesive (PIEA) with high strength, toughness, self-healing abilities, and ionic conductivity is synthesized by copolymerizing hydrophobic ionic liquid monomer ([HPVIm][TFSI]) and 2-methoxyethyl acrylate (MEA). The adhesion strength of PIEA can increase spontaneously from almost no adhesion to 314 kPa after 12 h without any external preloading due to the dissociation of the borate ester in water, leading to noncovalent interactions between the hydroxyl groups of PIEA and the substrate. Additionally, PIEA can be developed for soft sensors or ion electrodes to enable underwater detection and communication. This strategy offers broad application potential for the development of novel underwater smart adhesives.

Adhesion Evolution: Designing Smart Polymeric Adhesive Systems with On-Demand Reversible Switchability.

Smart polymeric switchable adhesives represent a rapidly emerging class of advanced materials, exhibiting the ability to undergo on-demand transitioning between "On" and "Off" adhesion states. By selectively tuning external stimuli triggers (including temperature, light, electricity, magnetism, and chemical agents), we can engineer these materials to undergo reversible changes in their bonding capabilities. The strategic design selection of stimuli is a pivotal factor in the design of switchable adhesive systems. This review outlines recent advancements in the field of smart switchable polymeric adhesives over the past decade with a focus on the selection of stimulus triggers. These systems are further categorized into one of four adhesion switching mechanisms upon initiation by a specific stimuli-trigger: (i) interfacial adhesion, (ii) stiffness, (iii) contact area, or (iv) suction-based switching. Evaluation of adhesion switching performance across systems is primarily made based on three key metrics: (i) maximum adhesion strength, (ii) switch ratio, and (iii) switch time. Different stimuli and mechanisms offer distinct advantages and limitations, influencing the performance characteristics and applicability of these materials across domains such as detachable biomedical devices, robotic grippers, and climbing robots. This review thus offers a perspective on the present advancements and challenges in this emerging field, along with insights into future directions.

Tremendous Stiffness‐Changing Polymer Networks Enabled by Touch‐Induced Crystallization

AbstractStiffness‐changing polymers are critically needed for intelligent and adaptive applications in soft robotics and wearable electronics; however, they suffer from the requirement of persistent external stimulation. Herein, a stiffness‐changing polymer network impregnated with a supercooled ionic liquid is introduced, which undergoes touch‐induced crystallization from a soft ionogel to a stiff plastic. The network exhibits a remarkable tunability in stiffness change, with the highest value exceeding 190 000 times between the soft and stiff states (3.5 kPa vs 691.1 MPa). This tremendous transition is achieved through the first‐order liquid–solid phase transition of the supercooled ionic liquid, which is highly reversible and isochoric via a heating‐cooling process. Unlike traditional stimuli, only a single touch is needed without sustained stimulation to trigger the stiffening from soft to stiff states. Importantly, the touch‐responsive polymer network can be extended to various types of ionic liquids and monomers, indicating excellent strategic versatility. Moreover, this unique ionogel exhibits switchable adhesiveness and ionic conductivity, effectively demonstrating smart adhesives and ionic switches with enhancements of more than 66 and 5800 times, respectively. This work provides a facile and versatile strategy for designing stable stiffness‐changing polymers, unlocking significant potential applications for next‐generation smart devices.

Fibrillar adhesives with unprecedented adhesion strength, switchability and scalability.

Bio-inspired fibrillar adhesives have received worldwide attention but their potentials have been limited by a trade-off between adhesion strength and adhesion switchability, and a size scale effect that restricts the fibrils to micro/nanoscales. Here, we report a class of adhesive fibrils that achieve unprecedented adhesion strength (∼2MPa), switchability (∼2000), and scalability (up to millimeter-scale at the single fibril level), by leveraging the rubber-to-glass (R2G) transition in shape memory polymers (SMPs). Moreover, R2G SMP fibrillar adhesive arrays exhibit a switchability of >1000 (with the aid of controlled buckling) and an adhesion efficiency of 57.8%, with apparent contact area scalable to 1000mm2, outperforming existing fibrillar adhesives. We further demonstrate that the SMP fibrillar adhesives can be used as soft grippers and reusable superglue devices that are capable of holding and releasing heavy objects >2000 times of their own weight. These findings represent significant advances in smart fibrillar adhesives for numerous applications, especially those involving high-payload scenarios.

Skin Temperature-Triggered Switchable Adhesive Coatings for Wearing Comfortable Epidermal Electronics

Smart adhesives with switchable adhesion strength on demand are crucial for ensuring the stability of the epidermal electronics-skin interface and preventing skin damage caused by device detachment. However, challenges such as harsh triggering conditions, lack of precise control over material comprehensive performance, and difficulty in achieving micron-level controlled integration of materials on device surfaces hinder the application of switchable adhesives in epidermal electronics. Herein, we designed a coatable, thermally-triggered switchable adhesive that has a high adhesion of 68.8 N/m at skin temperature, e.g., 33 °C, and after a slight cooling, e.g., 20 °C, the adhesion decreases to 6.59 N/m, resulting in a high switching ratio of 10.4. The switching time is < 1 min. This unique property is achieved by combining side-chain crystalline polymers and self-adhesive polymers through a strategy of constructing core–shell particles. The results of thermal analyses, rheology, and solid-state nuclear magnetic resonance indicate that a rapid and reversible crystallization-melting transition within the material is the essence of the adhesion switching. By depositing the material on flexible electrodes using spraying technology, we have obtained an ultra-thin (<5 μm), and peelable on-demand epidermal electrode, demonstrating the advantages of emulsion materials in the fabrication of wearing comfortable devices.

Electrically active smart adhesive for a perching-and-takeoff robot.

Perching-and-takeoff robot can effectively economize onboard power and achieve long endurance. However, dynamic perching on moving targets for a perching-and-takeoff robot is still challenging due to less autonomy to dynamically land, tremendous impact during landing, and weak contact adaptability to perching surfaces. Here, a self-sensing, impact-resistant, and contact-adaptable perching-and-takeoff robot based on all-in-one electrically active smart adhesives is proposed to reversibly perch on moving/static dry/wet surfaces and economize onboard energy. Thereinto, attachment structures with discrete pillars have contact adaptability on different dry/wet surfaces, stable adhesion, and anti-rebound; sandwich-like artificial muscles lower weight, enhance damping, simplify control, and achieve fast adhesion switching (on-off ratio approaching ∞ in several seconds); and the flexible pressure (0.204% per kilopascal)-and-deformation (force resolution, <2.5 millinewton) sensor enables the robot's autonomy. Thus, the perching-and-takeoff robot equipped with electrically active smart adhesives exhibits tremendous advantages of soft materials over their rigid counterparts and promising application prospect of dynamic perching on moving targets.

Autonomous underwater adhesion driven by water-induced interfacial rearrangement

Underwater adhesives receive extensive attention due to their wide applications in marine explorations and various related industries. However, current adhesives still suffer from excessive water absorption and lack of spontaneity. Herein, we report an autonomous underwater adhesive based on poly(2-hydroxyethyl methacrylate-co-benzyl methacrylate) amphiphilic polymeric matrix swollen by hydrophobic imidazolium ionic liquid. The as-prepared adhesive is tough and flexible, showing little to none instantaneous underwater adhesion onto the PET substrate, whereas its adhesion energy on the substrate can grow more than 5 times to 458 J·m−2 after 24 hours. More importantly, this process is entirely spontaneous, without any external pressing force. Our comprehensive studies based on experimental characterizations and molecular dynamic simulations confirm that such autonomous adhesion process is driven by water-induced rearrangement of the functional groups. It is believed that such material can provide insights into the development of next-generation smart adhesives.

Polydopamine-Modified MXene-Integrated Poly(N-isopropylacrylamide) to Construct Ultrafast Photoresponsive Bilayer Hydrogel Actuators with Smart Adhesion.

In nature, living organisms, such as octopuses, cabrito, and frogs, have already evolved admirable adhesive abilities for better movement and predation in response to the surroundings. Inspired by biological structures, researchers have made enormous efforts in developing actuators that can respond to external stimuli, while such adhesive property is very desired, yet there is still limited research in responsive hydrogel actuators. Here, a bilayer actuator with high stretchability and robust interface bonding is presented, which has a smart adhesion and thermoreception function. The system consists of an adhesive passive layer copolymerized of amphoteric ([2-(methacryloyloxy) ethyl] dimethyl-(3-sulfopropyl), SBMA) and acrylic acid (AA), and an active layer hydrogel composed of poly(N-isopropylacrylamide) (PNIPAm) containing polydopamine-modified MXene (P-MXene) and calcium chloride (CaCl2). The coordination of carboxylate and Ca2+ at the interface of the two layers enhances the interfacial bonding from 14 to 30 N m-1, which facilitates withstanding large strain and preventing stratification. The resulting hydrogel actuator can bend approximately 360° in a mere 10 s, exhibiting excellent photothermal effect, a large angle bending deformation, and ultrafast photoresponsive ability. As a proof of concept, the photothermal actuators are programmed to present various shapes and grab objects. Importantly, the hydrogel actuator exhibits remarkable adhesion capabilities toward diverse substrates, with a maximum peel force of up to 280 N m-1. Relying on their own adhesion and the photoresponse properties, these flexible adhesion actuators show outstanding gripping capability, enabling them to grip and release objects of different shapes and weights. More interestingly, the hydrogel exhibits a smart adjustable adhesion capability at different temperatures, which enables it as a gripper to recognize temperature signals through real-time different feedback actions based on its own adhesion. This study presents innovative insights into biomimetic hydrogel actuators, providing new opportunities for developing intelligent soft robots with multiple functions.

Development of hydrophobic, mechanically reliable, and glow-in-the-dark glue using Arabic gum.

A smart nanocomposite adhesive was created to facilitate a simple production of long-persistent photoluminescent and hydrophobic commercial products. Even after being left in the dark for up to 90 min, the created photoluminescent adhesive agent continued to generate light. A surface-specific nanocomposite adhesive agent consisting of lanthanide-activated strontium aluminate (LSA) nanoparticles (NPs; 5-14 nm) immobilized in the environmentally friendly Arabic gum (AG) was developed. A light-transmitting nanocomposite adhesive agent was manufactured by dispersing LSA nanoparticles evenly across the AG matrix without agglomeration. An excitation peak at 365 nm and an emission wavelength at 519 nm were observed for the prepared adhesives at different concentrations of LSA NPs. The emission spectra showed either fluorescence or afterglow phosphorescence, depending on the LSA ratio. The photochromic transition from colourless to green beneath an ultraviolet (UV) lamp and greenish yellow in a dark room was tracked. The LSA NPs in the Arabic gum matrix imparted enhanced hydrophobicity and scratch resistance to the LSA@AG nanocomposite. The LSA@AG nanocomposite demonstrated excellent durability and photostability. This study confirmed that the mass production of smart adhesives for applications such as smart windows, smart packaging, and safety directional signs in buildings is possible.

Mussel-inspired hydrogels with UCST for temperature-controlled reversible adhesion

Achieving on-demand adhesion on different surfaces remains an adaunting challenge for polymer adhesives. Herein, we report a temperature-controlled adhesion strategy of hydrogels based on the reversible exposure and shielding of adhesive promoters regulated by microphase separation. The hydrogels are constructed by the physical crosslinking (hydrogen bonding and ion interaction) of a ternary random copolymer (PQAM) derived from the copolymerization of catechol containing quaternary ammonium salt monomer (QCA), acrylic acid (AA), and acrylamide (AAm). The physically crosslinked polymer networks can effectively toughen the hydrogels, resulting in tensile fracture strength, elongation, and energy up to 43.3 kPa, 1223%, and 9.5 kJ/m2, respectively. PQAM hydrogels exhibit upper critical solution temperature (UCST) behavior, and the transition temperature can be easily adjusted from 42.1 to 49.0 °C by changing the content of PQCA. PQAM hydrogels are non-transparent and non-adhesive at temperatures below UCST, while become transparent and highly adhesive at temperatures above UCST. By simply controlling the temperature, PQAM hydrogels can repeatedly attach to and detach from various substrates (including glass, plastics, ceramic, rock, wood, and metal) with an optimal adhesion strength up to 35.5 kPa. The strategy of hiding adhesive promoters may be interesting in the design of smart adhesives.

Mechanics of Tunable Adhesion With Surface Wrinkles

Abstract Surface wrinkles have emerged as a promising avenue for the development of smart adhesives with dynamically tunable adhesion, finding applications in diverse fields, such as soft robots and medical devices. Despite intensive studies and great achievements, it is still challenging to model and simulate the tunable adhesion with surface wrinkles due to roughened surface topologies and pre-stress inside the materials. The lack of a mechanistic understanding hinders the rational design of these smart adhesives. Here, we integrate a lattice model for nonlinear deformations of solids and nonlocal interaction potentials for adhesion in the framework of molecular dynamics to explore the roles of surface wrinkles on adhesion behaviors. We validate the proposed model by comparing wrinkles in a neo-Hookean bilayer with benchmarked results and reproducing the analytical solution for cylindrical adhesion. We then systematically study the pull-off force of the wrinkled surface with varied compressive strains and adhesion energies. Our results reveal the competing effect between the adhesion-induced contact and the roughness due to wrinkles on enhancing or weakening the adhesion. Such understanding provides guidance for tailoring material and geometry as well as loading wrinkled surfaces for different applications.

A Janus supramolecular hydrogel prepared by one-pot method for wound dressing

Despite the adhesive hydrogels have gained progress and popularity, it is still an enormous challenge to develop a smart adhesion hydrogel for clinical medicine, which is an asymmetric adhesion hydrogel with on-demand detachment. Motivated by the thermal phase transition mechanism of gelatin, we have synthesized a Janus supramolecular hydrogel dressing with skin temperature-triggered adhesion by a simple one-pot process. This hydrogel has asymmetric and controllable adhesion, which not only can become the external objects barrier but also can achieve repeated adhesion and on-demand detachment triggered by temperature in tens of seconds. This hydrogel presents great mechanical performance (compressive strain of 65 %, 1.38 MPa) owing to the presence of supramolecular interactions in the hydrogel. Additionally, this hydrogel exhibits excellent antibacterial activity and biocompatibility. The synergistic effect of modified gelatin and ionic liquid greatly facilitates wound healing of full-thickness skin with high wound healing efficiency (98.45 %). Therefore, thanks to all these advantages, the Janus supramolecular hydrogel can be applied for wound management and treatment, which has huge potential in healing skin wounds.

Light‐controlled switchable underwater adhesive

AbstractDespite extensive efforts in designing and preparing switchable underwater adhesives, it is not easy to regulate the underwater adhesion strength locally and remotely. Here, we design and synthesize photoreversible copolymer of poly[dopamine methacrylamide‐co‐methoxyethyl‐acrylate‐co‐7‐(2‐methacryloyloxyethoxy)‐4‐methylcoumarin]. Due to the dynamic formation and breaking of chemical crosslinking networks within the smart adhesives, the material shows widely tunable adhesion strength from ∼150 to ∼450 kPa and long‐range reversible maneuverability under orthogonal 254 and 365 nm ultraviolet light stimulation via the coumarin dimerization and cycloreversion. Moreover, the adhesive exhibits good circulation performance and stability in an acid–base environment. It also demonstrated that the bolt can be coated with the smart adhesive material for on‐demand bonding. This design principle opens the door to the development of remotely controllable high‐performance smart underwater adhesives.

Robust and smart underwater adhesion of hydrophobic hydrogel by phase change

Water-durable adhesives are widely explored in various fields like wearable electronics, tissue engineering and sea refloatation. However, in harsh underwater environment, adhesives with sound and comprehensive performance on various surfaces remain highly challenging. Herein, we report a hydrophobic hydrogel adhesive composed of crystalline octadecyl (C18) chains with versatile, robust and thermally switchable underwater adhesion. The inherent hydrophobicity and the amorphous state of C18 chains allow the hydrogel adhesive to conformally adapt to underwater surfaces, independent of surface energy, curvature, charge and roughness as well as the salinity and pH of the water environment. The crystallization of C18 chains greatly increases the modulus of the hydrogel, interlocking the adhesive to the contacting surfaces and resulting in the underwater adhesion up to 275 kPa. The phase change of hydrogel regulates the stress distribution at the contact interface and the adhesion capacity, resulting in a switchable underwater adhesion. The phase change of C18 chains also endows the hydrogel self-healing property, ensuring durability and reusability. Moreover, the temperature of phase change is around ∼ 40 ℃, endowing adhesive with bio-applications in dynamic watery environments. Therefore, the adhesive is highly potential in emerging areas of wearable electronics, tissue engineering and so on.

Superhydrophobic TiO2 nanotube arrays with switchable adhesion in both air and oil

Superhydrophobic surfaces with smart adhesion has aroused increased interest. However, all reported surfaces can only display switchable adhesion in air. Herein, we report a fluoroalkylsilane-modified TiO2 nanotube surface that has switchable adhesion in both air and oil as it is alternately Ultraviolet-irradiated and heated. The transition is not synchronous; a longer Ultraviolet-irradiation time is needed to obtain high adhesion in oil than in air, and the transition is more difficult in polar oil than in non-polar oil. The reversible transition attributes to the combined effect between the nanostructure and surface chemical variation, the out-of-step transition is attributed to different roles of the exposed naked TiO2, which offers water-adhesive force in air and oil-adhesive/water-repellent force in oil. This works reveals the effect of environmental media on surface-wetting/adhesion transition, which is helpful for design of novel adhesive surfaces to meet practical requirements.

Electrochemical Deactivation of Switchable Catechol-Containing Smart Adhesive from Nonconductive Surfaces

The feasibility of deactivating and reactivating a catechol-containing smart adhesive electrochemically while in direct contact with a nonconductive surface was explored in this work. The adhesive was coated over an aluminum mesh-attached poly(dimethylsiloxane) (AM-PDMS) substrate. The aluminum mesh served as an electrode to apply electricity through the adhesive. A silver (Ag) counter electrode was coated in the periphery of the adhesive–substrate interface to deactivate the adhesive attached to the nonconductive surfaces including glass and poly(methyl methacrylate) (PMMA) substrates. The deactivation of the adhesive was performed with the application of up to 20 V of applied electricity utilizing the Ag electrode as a cathode and the aluminum mesh as an anode. The adhesion strength of the adhesive toward nonconductive surfaces decreased by 98% after in situ application of electricity. The deactivation rate was tunable with the applied voltage level, exposure time to the applied voltage, surface area of the adhesive interface, and aluminum mesh size. The deactivated adhesive was reactivated electrochemically by reversing the electrode polarity up to 3 cycles utilizing catechol–boronate complexation chemistry.

Overcoming the adhesion paradox and switchability conflict on rough surfaces with shape-memory polymers

Smart adhesives that can be applied and removed on demand play an important role in modern life and manufacturing. However, current smart adhesives made of elastomers suffer from the long-standing challenges of the adhesion paradox (rapid decrease in adhesion strength on rough surfaces despite adhesive molecular interactions) and the switchability conflict (trade-off between adhesion strength and easy detachment). Here, we report the use of shape-memory polymers (SMPs) to overcome the adhesion paradox and switchability conflict on rough surfaces. Utilizing the rubbery-glassy phase transition in SMPs, we demonstrate, through mechanical testing and mechanics modeling, that the conformal contact in the rubbery state followed by the shape-locking effect in the glassy state results in the so-called rubber-to-glass (R2G) adhesion (defined as making contact in the rubbery state to a certain indentation depth followed by detachment in the glassy state), with extraordinary adhesion strength (>1 MPa) proportional to the true surface area of a rough surface, overcoming the classic adhesion paradox. Furthermore, upon transitioning back to the rubbery state, the SMP adhesives can detach easily due to the shape-memory effect, leading to a simultaneous improvement in adhesion switchability (up to 103, defined as the ratio of the SMP R2G adhesion to its rubbery-state adhesion) as the surface roughness increases. The working principle and the mechanics model of R2G adhesion provide guidelines for developing stronger and more switchable adhesives adaptable to rough surfaces, thereby enhancing the capabilities of smart adhesives, and impacting various fields such as adhesive grippers and climbing robots.

Sequential self-assembly and self-coacervation actuate water-triggered robust bonding: From universal underwater adhesion to on-demand detachable bioadhesion

Achieving strong and long-lasting underwater adhesion remains a great challenge because both interfacial hydration film and continuous water erosion significantly impede the interfacial bonding. Herein, a sequential self-assembly and self-coacervation strategy was proposed to actuate water-triggered robust underwater bonding to both abiotic materials and biological tissues. With the embedded polyhedral oligomeric silsesquioxane (POSS) cages serving as rigid and hydrophobic segments, the amphiphilic hybrid hyperbranched polymer featured conformation variation capacity under the synergy of sharply decreased solubility and cluster effect of polyfunctional groups on POSS cages. The polymer firstly altered conformation into an assembled adhesive with extremely rigid hydrophobic POSS clusters for significantly enhancing the cohesion. Once touching water, the prompt aggregation of POSS clusters and followed self-coacervation behavior of the adhesive boosted interfacial water expulsion and catechol groups exposure, resulting in spontaneous solidification and universally eminent underwater adhesion between the adhesive and diverse substrates. The adhesive not only exhibited outstanding adhesive performances in water, seawater, PBS, acid, and alkali solutions, but also possessed excellent anti-erosion capacity to demonstrate long-lasting underwater adhesion for months. Prominently, a smart bioadhesive was developed via introducing tissue adhesive group and sensitive disulfide bond, which revealed strong adhesion to wet tissues and on-demand debonding capacity. The water-triggered robust and long-lasting underwater bonding mediated by sequential self-assembly and self-coacervation opens up a new horizon in the design and progress of smart and high-performance underwater adhesives.

Beetle-inspired oil-loaded shape memory micro-arrays with switchable adhesion to both solid and liquid

Surfaces with switchable adhesion have been vigorously investigated over the past decades by mimicking the unique adhesive mechanisms of living systems. However, designing a universal intelligent adhesive surface for both solid and liquid remains a challenge. Herein, drawing inspiration from the controllable capillary forces generated by muscle movements and oil-secretion on the foot pads of the beetle (Hemisphaerota cyanea), we report a novel oil-loaded shape memory polymer (SMP) micropillars with such smart controllability. Based on the shape memory effect (SME) of the SMP, the pillars can be reversibly switched between the tilted state and the upright state, which simultaneously changes the distribution of the trapped oil, and thus generates different capillary forces. This variation results in reversible adhesion behaviors of the surface to diverse solids including flat glass, CD disk, polytetrafluoroethylene (PTFE), rough glass, sandpaper, nylon net, and liquid droplets like acid, basic, salt-containing water droplets, and some organic liquids such as glycol, glycerol, and formamide. Given its smart adhesion, the surface was further applied in in-situ gripping/release of solid objects and directed liquid shedding. This work provides a new design strategy for smart adhesive materials, which may contribute to the development of smart grippers, microfluidics, etc.